TWI564354B - Photo-curable coating composition, photo-curing coating film and touch panel - Google Patents

Description

Photocurable coating composition, photocurable coating film, and touch panel

The present invention relates to a photocurable coating composition, and more particularly to a photocurable coating composition comprising a photocurable polymer having a polyorganometalloxane structure and a polyamidene structure. (Photo-curable composition), a photocurable coating film obtained from the photocurable coating composition, and a touch panel including the photocurable coating film.

Recently, in order to achieve high refractive index, high transmittance, good protection, and good visibility, a photocurable composition has been developed which can be used in various display devices, which are formed by such a photocurable composition. The photohardenable coating film layer also functions as an overcoat layer and a bismuth pentoxide (Nb ₂ O ₅ ) layer.

However, as electronic products increasingly emphasize flexibility, the use of flexible displays has also attracted attention. In a flexible display, a conventional glass substrate is replaced by a plastic substrate, such as a polyimide (PI) substrate. However, when the photocurable composition is used in a flexible display, there is a problem that the adhesion to the polyimide substrate is poor. question.

The present invention provides a photocurable coating composition which has good refractive index, dispersibility and coatability.

The present invention further provides a photocurable coating film which has good refractive index, adhesion, and chemical resistance.

The present invention further provides a touch panel having a light-curable coating film which is excellent in adhesion to a substrate.

The photocurable coating composition of the present invention comprises: a photocurable polymer having a polyorganometalloxane structure and a polyamidene structure, wherein the polyorganometallic ruthenium is based on 100 parts by weight of the photocurable polymer. The content of the oxyalkylene structure is from 60 parts by weight to 95 parts by weight, and the content of the polyamidene structure is from 5 parts by weight to 40 parts by weight. Moreover, the polyamidene structure has a ruthenium imidation ratio of 60% to 75%.

In one embodiment of the present invention, the polyorganometalloxane structure is contained in an amount of from 65 parts by weight to 90 parts by weight based on 100 parts by weight of the photocurable polymer, and the polyiminoimine structure is contained in an amount of 10 parts by weight. Parts by weight to 35 parts by weight.

In one embodiment of the present invention, the polyorganometalloxane structure is contained in an amount of 70 parts by weight to 90 parts by weight based on 100 parts by weight of the photocurable polymer, and the polyiminoimine structure is 10 parts by weight. Parts by weight to 30 parts by weight.

In an embodiment of the invention, the polyamidene structure has a ruthenium amination ratio of 60% to 69%.

In an embodiment of the invention, the photocurable coating composition described above may further include a solvent.

In one embodiment of the present invention, the polyorganometalloxane structure comprises a compound represented by the formula (I), the formula (II) and the formula (III) by hydrolysis and condensation reaction.

R ^a ₁ Si(OR ^b ) ₃ (I) In the formula (I), R ^a represents an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms having an acryloxy group or a methacryl The alkyl group having 1 to 5 carbon atoms of the oxy group; and R ^b represents an alkyl group having 1 to 5 carbon atoms.

Si(OR ^c ) ₄ (II) In the formula (II), R ^c represents an alkyl group having 1 to 5 carbon atoms.

M(OR ^d ) _n (III) In the formula (III), M represents titanium (Ti), cerium (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg) or zinc (Zn). And R ^d represents an alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 5.

Wherein the content of the compound represented by the formula (I) is from 25 parts by weight to 45 parts by weight based on 100 parts by weight of the compound represented by the formula (I), the formula (II) and the formula (III), The content of the compound shown in (II) is from 15 parts by weight to 20 parts by weight, and the content of the compound represented by the formula (III) is from 35 parts by weight to 60 parts by weight.

In one embodiment of the present invention, the compound represented by the above formula (I) includes vinyltrimethoxynonane, and at least one selected from the group consisting of 3-methacryloxypropyltrimethoxydecane and 3-methyl. Propylene oxiranyl triethoxy decane and 3-propenyl methoxypropyl trimethoxy decane.

The photocurable coating film of the present invention is obtained from the above photocurable coating composition.

In another embodiment of the present invention, the photocurable coating film has a refractive index of 1.60 to 1.65 at a film thickness of 100 nm.

The touch panel of the present invention includes the above-described photo-curing coating film.

Based on the above, the photocurable polymer in the photocurable coating composition of the present invention has a polyorganometalloxane structure and a polyamidene structure having a specific ratio, and a polyamidene structure. Since the photo-curable coating film produced by the above composition has a good refractive index, adhesion, and chemical resistance.

The above described features and advantages of the invention will be apparent from the following description.

100‧‧‧ touch panel

102‧‧‧Substrate

104‧‧‧Touch components

106‧‧‧Protective layer

110, 120‧‧‧ Touch series

112, 122‧‧‧ touch electrodes

114, 124‧‧‧ Connections

130‧‧‧Insulation pattern

D1, D2‧‧‧ direction

FIG. 1 is a top plan view of a touch panel according to an embodiment of the invention.

2 is a cross-sectional view of the touch panel of FIG. 1 taken along line I-I'.

Hereinafter, embodiments of the invention will be described in detail. However, these embodiments are illustrative, and the disclosure of the present invention is not limited thereto.

In an embodiment of the invention, the photocurable coating composition comprises light hard Polymer. The content of the polyorganometallosiloxane structure and the polyimide series structure is from 60 parts by weight to 95 parts by weight and 5 parts by weight, respectively, per 100 parts by weight of the photocurable polymer. Up to 40 parts by weight. When the content of the polyorganometalloxane structure is less than 60 parts by weight and the content of the polyamidene-based structure is more than 40 parts by weight, the solution dispersibility and the solution coating property are inferior. When the content of the polyorganometalloxane structure is more than 95 parts by weight and the content of the polyamidene-based structure is less than 5 parts by weight, the adhesion to the PI substrate is inferior. In another embodiment, the content of the polyorganometalloxane structure is 65 parts by weight to 90 parts by weight based on 100 parts by weight of the photocurable polymer, and the content of the polyamidene structure is 10 parts by weight to 35 parts by weight; preferably, based on 100 parts by weight of the photocurable polymer, the polyorganometalloxane structure is 70 parts by weight to 90 parts by weight, and the polyamidene structure is 10 parts by weight to 30 parts by weight.

Further, in the photocurable polymer, the polyamidene structure has a ruthenium amination ratio of 60% to 75%; preferably 60% to 69%. When the ruthenium iodide ratio is more than 75%, the solution coating property is poor; when the oxime imidization ratio is less than 60%, the obtained photocurable coating film is inferior in chemical resistance.

Polyorganometalloxane structure

In one embodiment, the polyorganometalloxane structure comprises a compound represented by the formula (I), the formula (II) and the formula (III) by hydrolysis and condensation reaction.

R ^a ₁ Si(OR ^b ) ₃ (I) In the formula (I), R ^a represents an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms having an acryloxy group or a methacryl The alkyl group having 1 to 5 carbon atoms of the oxy group; and R ^b represents an alkyl group having 1 to 5 carbon atoms.

Si(OR ^c ) ₄ (II) In the formula (II), R ^c represents an alkyl group having 1 to 5 carbon atoms.

M(OR ^d ) _n (III) In the formula (III), M represents titanium (Ti), cerium (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg) or zinc (Zn). And R ^d represents an alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 5, preferably an integer of 3 or 4.

The content of the compound represented by the formula (I) is from 25 parts by weight to 45 parts by weight based on 100 parts by weight of the compound represented by the formula (I), the formula (II) and the formula (III), and the formula (II) The content of the compound shown is from 15 parts by weight to 20 parts by weight, and the compound represented by the formula (III) is contained in an amount of from 35 parts by weight to 60 parts by weight.

The above "alkenyl group having 2 to 10 carbon atoms" may, for example, be a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group or a 1-pentenyl group. , 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl.

The above-mentioned "alkyl group having 1 to 5 carbon atoms having an acryloxy group or alkyl group having 1 to 5 carbon atoms having a methacryloxy group" may, for example, be 3-propenyloxypropyl or 3-methyl. Acryloxypropyl.

The above "alkyl group having 1 to 5 carbon atoms" may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or isopentyl.

Examples of the compound represented by the formula (I) include, but are not limited to, vinyl trimethoxysilane, vinyl triethoxysilane (vinyl) Triethoxysilane), 3-acryoyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane 3-methacryloyloxypropyl triethoxysilane, or a combination thereof. Further, examples of commercially available products suitable for use as the compound represented by the general formula (I) include: KBM 1003, KBE 1003, KBM 503, KBE 503, and KBM 5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the compound represented by the formula (II) include, but are not limited to, tetraalkoxydecanes such as tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane; or a combination thereof.

Examples of the compound represented by the formula (III) include, but are not limited to, titanium alkoxide, and tetraalkyltitanium oxide compound such as tetraethoxytitanium oxide, tetrapropylene titanium oxide, tetraisobutyltitanium oxide or tetra-n-butyltin oxide can be used. As the zirconium alkoxide, a tetradecyl zirconia compound such as tetraethoxy zirconia, tetrapropoxide zirconia or tetrabutyl zirconia; aluminum alkoxide, tributyl alumina, triisopropyl alumina, triethoxylate can be used; A trialkylaluminum compound such as aluminum; a nonane oxide; a pentadecane ruthenium compound such as pentapropoxide or pentoxide, or a combination thereof may be used.

The compound represented by the above formula (I) may include vinyl trimethoxysilane, and at least one selected from the group consisting of 3-methacryloxypropyltrimethoxydecane, from the viewpoint of improving hardness. 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl triethoxysilane and 3-propenyloxypropyl trimethylsilane 3-acryloyloxypropyl trimethoxysilane.

In the foregoing embodiments, the hydrolysis method can be carried out by a general method. For example, a compound represented by the formula (I), a compound represented by the formula (II), and a compound represented by the formula (III) and a solvent, water or a catalyst optionally added at 30 ° C to 150 Heat and stir at °C for 0.5 hour to 120 hours. Further, by stirring, by-products (e.g., alcohols, water, etc.) may be further removed by distillation.

The solvent is not particularly limited and may be the same as or different from the solvent used in the photocurable coating composition of the present invention (the description will be described later) as long as it is a soluble reactant and a product. The solvent is preferably used in an amount of 100 parts by weight based on 100 parts by weight of the total of the compound represented by the formula (I), the compound of the formula (II) and the compound of the formula (III). 1,200 parts by weight, more preferably from 300 parts by weight to 1,000 parts by weight.

The hydrolyzable water contained in the compound represented by the formula (I), the compound represented by the formula (II) and the compound represented by the formula (III) is 1 mol. The amount used is from 0.5 moles to 2 moles.

The above catalyst is not particularly limited. In one embodiment, the catalyst is selected from an acid catalyst or a base catalyst. The acid catalyst includes, but is not limited to, oxalic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, ion exchange resin, and the like. The base catalyst includes, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, an alkoxysilane containing an amine group, an ion exchange resin, and the like. a compound represented by the formula (I), a compound represented by the formula (II), and a compound The total amount of the compound represented by the formula (III) is 100 parts by weight, and the amount of the catalyst used is preferably from 0.005 parts by weight to 15 parts by weight, more preferably from 0.01 part by weight to 12 parts by weight, most preferably 0.05 parts by weight. Up to 10 parts by weight.

From the viewpoint of stability, the polyorganometalloxane polymer obtained by the hydrolysis condensation reaction is preferably free from by-products (such as alcohols or water) and a catalyst, so that it can be selectively hydrolyzed and condensed. The polyorganometalloxane polymer obtained by the reaction is purified. The purification method is not particularly limited. In one embodiment, the polyorganometalloxane polymer can be diluted with a hydrophobic solvent, followed by concentration of the organic layer washed several times with water by an evaporator to remove the alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.

Polyimine structure

In one embodiment, the polyimine structure comprises a structure in which a tetracarboxylic dianhydride and a diamine are subjected to a polymerization reaction and a dehydration ring closure reaction.

The tetracarboxylic dianhydride is not limited and may be selected from an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and the following formula (a1) to formula A tetracarboxylic dianhydride compound represented by (a6) or a fluorine-containing tetracarboxylic dianhydride compound.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, an aliphatic tetracarboxylic dianhydride such as ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic acid Anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloheptyl-1,5- An alicyclic tetracarboxylic dianhydride compound such as diene-1,2,5,6-tetracarboxylic dianhydride or 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

The alicyclic tetracarboxylic dianhydride compound may also contain a bicyclo-containing aliphatic tetracarboxylic dianhydride compound. Preferably, the bicyclic alicyclic tetracarboxylic dianhydride compound has a bridged hydrocarbon group having a total atomic number of 7 to 9, and one of the tetravalent bridge hydrocarbon groups (bridge) The number of bridge atoms is 1 or 2.

Specific examples of the bicyclic alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-azabicyclo[2.2. 1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 7-thia Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 6-(carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid-2 ,3,5,6-dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5 ,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-5-ene-1,2,7,8-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-2-ene-2,3 ,5,6-tetracarboxylic dianhydride, 7-azabicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo[2.2.2]octane -2,3,5,6-tetracarboxylic dianhydride, 7-thiabicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[3.2.1]octane -2,3,5,6-tetracarboxylic dianhydride, bicyclo[3.2.1]octane-2,4,5,6-tetracarboxylic dianhydride, 7-azabicyclo[3.2.1]octane -2,3,5,6-tetracarboxylic dianhydride, 7-azabicyclo [3.2.1] Octane-2,4,5,6-tetracarboxylic dianhydride, 7-oxabicyclo[3.2.1]octane-2,3,5,6-tetracarboxylic dianhydride, 7 -oxabicyclo[3.2.1]octane-2,4,5,6-tetracarboxylic dianhydride, 7-thiabicyclo[3.2.1]octane-2,3,5,6-tetracarboxylic acid Dihydride, 7-thiabicyclo[3.2.1]octane-2,4,5,6-tetracarboxylic dianhydride, bicyclo[3.2.2]nonane-2,3,6,7-tetracarboxylic acid Dihydride, bicyclo[3.2.2]nonane-2,4,6,7-tetracarboxylic dianhydride, bicyclo[3.2.2]non-8-alkenyl-2,3,6,7-tetracarboxylic acid Dihydride, bicyclo[3.2.2]non-8-alkenyl-2,4,6,7-tetracarboxylic dianhydride, 8-azabicyclo[3.2.2]nonane-2,3,6,7 -tetracarboxylic dianhydride, 8-azabicyclo[3.2.2]nonane-2,4,6,7-tetracarboxylic dianhydride, 8-oxabicyclo[3.2.2]nonane-2,3 6,6-tetracarboxylic dianhydride, 8-oxabicyclo[3.2.2]nonane-2,4,6,7-tetracarboxylic dianhydride, 8-thiabicyclo[3.2.2]decane -2,3,6,7-tetracarboxylic dianhydride or 8-thiabicyclo[3.2.2]nonane-2,4,6,7-tetracarboxylic dianhydride or the like.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'- Biphenyl fluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-di Phenylethane tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic acid Dihydride, 1,2,3,4-furantetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether Tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylate Acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide On - stretch Phenyl-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl Ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis (dehydrated trimellitic acid) Ester), 1,4-butanediol-bis(anhydrotrimellitic acid ester), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-double (dehydration) Trimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitic acid ester), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c ]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl) )-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5 -di-oxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl -5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-di 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c ]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl )-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro- 2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-di-oxytetrahydrofuranyl)-3 -methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or the like.

The tetracarboxylic dianhydride represented by the formula (a1) to the formula (a6) is as follows:

In the formula (a5), A ₁ represents a divalent group containing an aromatic ring; a represents an integer of 1 to 2; and A ₂ and A ₃ may be the same or different and each may represent a hydrogen atom or an alkyl group. Preferably, the tetracarboxylic dianhydride represented by the formula (a5) may be selected from the compounds represented by the following formulas (a5-1) to (a5-3):

In the formula (a6), A ₄ represents a divalent group containing an aromatic ring; and A ₅ and A ₆ may be the same or different and each represents a hydrogen atom or an alkyl group. Preferably, the tetracarboxylic dianhydride represented by the formula (a6) may be selected from the compounds represented by the following formula (a6-1):

Specific examples of the fluorine-containing tetracarboxylic dianhydride compound may include, but are not limited to, 9,9-bis(trifluoromethyl)-9H-dibenzofuran-2,3,6,7-tetracarboxylic dianhydride. a tetracarboxylic dianhydride compound represented by the following formula (a7) to formula (a13) or any combination of the above compounds:

In the formula (a7), at least one of A ₇ and A ₈ is a fluorine atom or a trifluoromethyl group.

The above tetracarboxylic dianhydride may be used singly or in combination of plural kinds. The tetracarboxylic dianhydride preferably includes, but is not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, bicyclo [ 2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [ 2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 8-thiabicyclo[3.2.2]nonane-2,3,6,7-tetracarboxylic dianhydride , 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, benzene tetracarboxylic dianhydride, 3,3',4,4'-benzophenone IV Carboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 9,9-bis (three Fluoromethyl)-9H-dibenzofuran-2,3,6,7-tetracarboxylic dianhydride, 1,4-difluoro-2,3,5,6-benzenetetracarboxylic dianhydride, 3 , 6-bis(trifluoromethyl)-1,2,4,5-benzenetetracarboxylic dianhydride, or a tetracarboxylic dianhydride compound represented by the formula (a8) or the formula (a10).

The diamine is not limited and may be selected from an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound represented by the following formulas (b1) to (b15) or a fluorine-containing compound. A diamine compound or the like, and the above diamine may be used alone or in combination of plural kinds.

The aliphatic diamine compound includes, but is not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 4, 4'-Diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamine Base-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-di Amino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like.

The alicyclic diamine compound includes, but is not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-two Aminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.0 ^2,7 ]-ten Monocarbene dimethyl diamine, 4,4'-methylene bis(cyclohexylamine), and the like.

Aromatic diamine compounds include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylanthracene, 4 , 4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amine 1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino-1-(4'-aminophenyl)-1,3,3-tri Methylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone , 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- Aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3) -aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 9,10-bis(4-aminophenyl)anthracene [9,10-bis (4 -aminophenyl)anthracene], 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 4,4 '-(p-phenylphenylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 5-[4-(4-n-pentylcyclohexyl) Cyclohexyl]phenylmethylene-1,3-diaminobenzene {5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diami nobenzene}, 1,1-bis[4- (4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane {1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl) Cyclohexane} and so on.

The diamine compounds represented by the formulae (b1) to (b15) are as follows:

In the formula (b1), B ₁ represents -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-; B ₂ represents a steroid-like (steroid) skeleton having a carbon number of 2 to The alkyl group of 30 or a monovalent group derived from a cyclic structure of a nitrogen atom such as pyridine, pyrimidine, triazine, piperidine or piperazine.

The diamine compound represented by the formula (b1) is preferably selected from the group consisting of 2,4-diaminophenyl ethyl formate and 3,5-diaminophenylethylate B. 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5- Diaminophenyl propyl formate), 1-dodecoxy-2,4-aminobenzene, 1-hexadecyloxy-2,4-aminobenzene (1- Hexadecoxy-2,4-aminobenzene), 1-octadecoxy-2,4-aminobenzene or the following formula (b1-1) to formula (b1-4) Diamine compounds shown:

In the formula (b2), B ₃ represents -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-; B ₄ and B ₅ represent an extended aliphatic ring, an extended aromatic ring or a heterocyclic group; B ₆ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a cyano group or a chlorine atom. Preferably, the diamine compound represented by the formula (b2) is a diamine compound selected from the following formulas (b2-1) to (b2-8):

In the formulae (b2-5) to (b2-8), b may represent an integer of from 3 to 12.

In the formula (b3), B ₇ represents hydrogen, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a chlorine atom, and each repeat B ₇ in the unit may be the same or different; B ₈ is an integer from 1 to 3.

The diamine compound represented by the formula (b3) is preferably selected from the group consisting of (1) B ₈ being 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diamine toluene. Etc.; (2) B ₈ is 2:4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl , 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl or 2,2'-di Chloro-4,4'-diamino-5,5'-dimethoxybiphenyl, etc.; (3) B ₈ is 3: 1,4-bis(4'-aminophenyl)benzene, etc. Preferably selected from the group consisting of p-diamine benzene, 2,5-diamine toluene, 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl Or 1,4-bis(4'-aminophenyl)benzene.

In the formula (b4), B ₉ is an integer of 2 to 12.

In the formula (b5), B ₁₀ represents an integer of 1 to 5. The formula (b5) is preferably selected from 4,4'-diaminodiphenyl sulfide.

In the formula (b6), B ₁₁ and B ₁₃ may be the same or different and each represents a divalent organic group, and B ₁₂ represents a nitrogen-containing atom derived from a pyridine, a pyrimidine, a triazine, a piperidine or a piperazine. A divalent group of the structure.

In the formula (b7), B ₁₄ represents -O- or a cyclohexane group, B ₁₅ represents -CH ₂ -, B ₁₆ represents a phenyl or cyclohexane group, and B ₁₇ represents hydrogen or heptyl.

The diamine compound represented by the formula (b7) is preferably selected from the diamine compounds represented by the following formulas (b7-1) to (b7-2):

Other diamine compounds represented by formula (b8) to formula (b15) are as follows:

The fluorine-containing diamine compound is preferably selected from 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-amino) Phenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1 ,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-amine Phenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3 -hexafluoropropane, bis(2,3,5,6-tetrafluoro-4-aminophenyl)ether, bis(2,3,5,6-tetrafluoro-4-aminophenyl) sulfide, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, the following formula (b16) to a diamine compound of the formula (b45) or any combination of the above compounds:

The above diamines may be used singly or in combination of plural kinds. Preferably, the diamine includes, but is not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 4,4'-di Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-di Aminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, 2,4-diaminophenylformate B Ester, p-diamine benzene, m-diamine benzene, o-diamine benzene, 4,4'-diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl ]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, double ( 2,3,5,6-tetrafluoro-4-aminophenyl)ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, or formula (b1-1 ), formula (b1-2), formula (b2-1), formula (b2-6), formula (b7-1), formula (b23), formula (b25), formula (b26), formula (b27), a diamine compound represented by the formula (b33), the formula (b37) or the formula (b39).

In the foregoing embodiment, the method for producing the polyimine-based structural polymer comprises the steps of: dissolving a mixture comprising a tetracarboxylic dianhydride and a diamine in a solvent to carry out a polymerization reaction. Next, the above reaction solution is subjected to distillation under reduced pressure in an evaporator to obtain a polyamic acid resin, or the above reaction solution is poured into a large amount of a poor solvent to obtain a precipitate. Then, the precipitate is dried by a method of drying under reduced pressure to obtain a polyamine resin.

The tetracarboxylic dianhydride is preferably used in an amount of from 20 moles to 200 moles, more preferably from 30 moles to 120 moles, based on the total moles of the diamine being 100 moles.

The solvent used in the polymerization reaction may be the same as or different from the solvent used in the photocurable coating composition of the present invention (the description will be described later), and the solvent used in the polymerization reaction is not particularly specific. The restriction is as long as it is a soluble reactant and a product. Preferably, the total amount of the mixture of the tetracarboxylic dianhydride and the diamine is 100 parts by weight, and the solvent used in the polymerization is used in an amount ranging from 200 parts by weight to 2,000 parts by weight; more preferably, The solvent used in the polymerization is used in an amount ranging from 300 parts by weight to 1,800 parts by weight.

In particular, in the polymerization, the solvent may be used in combination with an appropriate amount of a poor solvent as long as the polyamic acid resin is not allowed to precipitate. The poor solvent may be used singly or in combination, and the poor solvent includes but is not limited to (1) alcohol: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohol or triethylene glycol; (2) ketones: acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; (3) esters: methyl acetate, ethyl acetate, acetic acid Ester, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers: diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, B Glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; (5) halogenated hydrocarbons: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene; (6) hydrocarbons: tetrahydrofuran, hexane, heptane, octane, Benzene, toluene or xylene, etc.; or (7) any combination of the above. Preferably, the total amount of the diamine used is 100 parts by weight, and the amount of the poor solvent is from 0 parts by weight to 60 parts by weight; more preferably, the amount of the poor solvent is from 0 parts by weight to 50 parts by weight. Share.

The preparation method of the polyamidene-based structural polymer further comprises the steps of: further heating the poly-proline resin formed by the polymerization reaction in the presence of a dehydrating agent and a catalyst, and performing a dehydration ring-closure reaction to cause a polymerization reaction. The resulting proline functional group is converted to a quinone imine functional group (ie, hydrazide).

The polymerization reaction and the dehydration ring closure reaction can employ a reaction temperature and a reaction time which have been conventionally operated in the art. Preferably, the polymerization has an operating temperature in the range of from 0 °C to 100 °C. Preferably, the polymerization has an operating time ranging from 1 hour to 24 hours. Preferably, the dehydration ring closure reaction has an operating temperature in the range of 30 ° C to 200 ° C, And the operation time of the dehydration ring closure reaction ranges from 0.5 hours to 50 hours.

The solvent used in the dehydration ring-closure reaction can be the same as the solvent used in the photocurable coating composition of the present invention, and therefore will not be described again. Preferably, the polyacetal acid resin is used in an amount of 100 parts by weight, and the solvent used in the dehydration ring closure reaction is used in an amount ranging from 200 parts by weight to 2,000 parts by weight, and more preferably, for the dehydration ring closure reaction. The solvent is used in an amount ranging from 300 parts by weight to 1,800 parts by weight.

The dehydrating agent used in the dehydration ring closure reaction is selected from the group consisting of (1) an acid anhydride compound: acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount ranging from 0.01 mol to 20 mol based on 1 mol of the polyaminic acid resin. The catalyst used in the dehydration ring closure reaction is selected from the group consisting of (1) a pyridine compound: pyridine, trimethylpyridine or lutidine; and (2) a tertiary amine compound: triethylamine. The catalyst is used in an amount ranging from 0.5 moles to 10 moles, based on the dehydrating agent being 1 mole.

In the photocurable polymer of the present invention, the ruthenium imidization ratio of the polyimine structure is 60% to 75%; preferably 60% to 69%. When the ruthenium iodide ratio is more than 75%, the solution coating property is poor; when the oxime imidization ratio is less than 60%, the obtained photocurable coating film is inferior in chemical resistance.

Solvent

In one embodiment, the solvent included in the photocurable coating composition is not particularly limited, and the solvent includes, but is not limited to, an alcoholic hydroxyl group-containing compound or a carbonyl group-containing cyclic compound. Further, the solvent may be used singly or in combination.

The alcoholic hydroxyl group-containing compound includes, but is not limited to, acetol (acetol), 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl- 2-pentanone (also known as diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethylether acetate, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol or a combination thereof . The alcoholic hydroxyl group-containing compound is preferably selected from the group consisting of diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, or a combination thereof.

The carbonyl group-containing cyclic compound includes, but is not limited to, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, nitrogen-methylpyrrolidone, cyclohexanone or cycloheptanone. The carbonyl-containing cyclic compound is preferably selected from the group consisting of γ-butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone, or a combination thereof.

The photocurable coating composition may contain other solvents within the range of the effect of not impairing the photocurable coating composition of the present invention. The other solvents include, but are not limited to, (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) ketones: methyl isobutyl ketone, diisopropanone, diisobutyl ketone, etc.; (3) ethers: diethyl ether, two Isopropyl ether, di-n-butyl ether, diphenyl ether, and the like.

Further, the solvent is preferably used in an amount of from 500 parts by weight to 20,000 parts by weight, more preferably from 800 parts by weight to 10,000 parts by weight, most preferably 1,000 parts by weight, based on 100 parts by total of the total amount of the photocurable polymer. 6,000 parts by weight.

Insofar as the effect of the photocurable coating composition of the present invention is not impaired, The photocurable coating composition may be added with other additives as needed. The additives may be used singly or in combination, and the additives include, but are not limited to, sensitizers, adhesion promoters, surfactants, dissolution promoters, antifoaming agents, or a combination thereof.

Light hardening coating film

In another embodiment of the present invention, the photocurable coating composition can be formed into a film by various suitable process techniques. For example, the photocurable coating composition is applied onto a substrate, pre-bake, photohardenable, and post-bake. Light hardened coating film. When the film thickness of the photo-curing coating film is 100 nm, the refractive index thereof is from 1.60 to 1.65.

The method of applying the photocurable coating composition is not limited, and a general coating method such as a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, or screen printing can be used. Method, inkjet method or offset printing method.

The temperature of the above prebaking treatment is, for example, room temperature to 150 ° C, preferably 40 ° C to 120 ° C. The pre-baking treatment time is, for example, about 30 seconds to 10 minutes, preferably about 1 minute to 8 minutes. The pre-baking treatment method is, for example, a hot plate or a hot air circulation type oven or the like.

The light used in the above photohardening treatment is exemplified by ultraviolet rays such as g-line, h-line, and i-line, and devices for providing ultraviolet rays such as (ultra) high-pressure mercury lamps, metal halide lamps, and the like.

The temperature of the post-baking treatment is, for example, 100 ° C to 300 ° C, preferably 150 ° C to 250 ° C. The post-baking treatment time is, for example, 5 minutes or longer, preferably 15 minutes. on. The post-baking treatment method uses, for example, a hot plate, a hot air circulation type oven, an infrared oven, or the like.

Touch panel

In still another embodiment of the present invention, the light-curable coating film can be used as one of members of a touch panel.

1 is a top plan view of a touch panel according to an embodiment of the present invention. 2 is a cross-sectional view of the touch panel of FIG. 1 taken along line I-I'. Referring to FIG. 1 and FIG. 2 , the touch panel 100 includes a substrate 102 , a touch element 104 , and a protective layer 106 .

Substrate 102 can be any substrate known in the art, such as a germanium substrate, a glass substrate, a plastic substrate, or other flexible substrate.

The touch element 104 is disposed on the substrate 102. In this embodiment, the touch component 104 includes a plurality of touch strings 110 and a plurality of touch strings 120, wherein the touch string 110 extends along the direction D1, and the touch string 120 intersects the direction D1. The direction D2 extends, and the touch string 110 and the touch string 120 are electrically insulated from each other. In detail, each touch string 110 includes a plurality of touch electrodes 112 and a plurality of connecting portions 114. Each of the connecting portions 114 connects two adjacent touch electrodes 112, and each touch string 120 includes multiple touches. The control electrode 122 and the plurality of connecting portions 124 are connected to the adjacent two touch electrodes 122. In addition, an insulation pattern 130 is disposed at the intersection of the touch string 110 and the touch string 120 to electrically insulate the two.

The material of the touch electrode 112 and the connecting portion 114 of the touch string 110 and the touch electrode 122 and the connecting portion 124 of the touch string 120 may be the same or different, and is, for example, a transparent conductive material or other suitable conductive material. Transparent conductive material The materials are, for example, indium tin oxide, indium zinc oxide, aluminum zinc oxide, and the like, and mixtures or laminates thereof.

In addition, in the present embodiment, the touch element 104 having the structure shown in FIGS. 1 and 2 is taken as an example, but the invention is not limited thereto. Touch element 104 can be any touch element known to those of ordinary skill in the art. That is, touch element 104 can have other configurations as are well known.

The protective layer 106 is disposed on the substrate 102 and covers the touch element 104 for protecting the touch element 104 from external force. In the present embodiment, the protective layer 106 is realized by the photo-curing coating film of any of the above embodiments. That is, the protective layer 106 is formed by applying the photocurable coating composition of the present invention to the touch element 104, and then performing prebaking treatment, photocuring treatment, and post-baking treatment. However, the related description and preparation method of the photo-curing coating film have been described in detail in the foregoing embodiments, and thus will not be described herein.

It is to be noted that, as described above, the refractive index coating film of the present invention has a refractive index of between 1.60 and 1.65, whereby the touch panel using the photohardenable coating film of the present invention as a protective layer can have a good performance. Visibility and display quality.

Several experiments are listed below to verify the effects of the present invention, but the scope of the present invention is not limited to the following experiments.

Preparation of polyorganometalloxane Raw material

VTMS: Vinyl trimethoxysilane

KBM503: 3-methacryloxypropyltrimethoxydecane (3-Methacryloxypropyl trimethoxysilane)

KBE503: 3-methacryloxypropyltriethoxydecane (3-Methacryloxypropyl triethoxysilane)

KBM5103: 3-Acryloxypropyl trimethoxysilane

TEOS: Tetraethoxysilane

TMOS: Tetramethoxysilane

Ti(OBu) ₄ : tetra-n-butoxy titanium

Ti(OEt) ₄ : tetraethoxy titanium

Ti(OPr) ₄ : titanium tetraisopropoxide

2. Synthesis Example A1

In a 500 ml three-necked flask, 20 parts by weight of vinyltrimethoxydecane (VTMS), 15 parts by weight of 3-methylpropenyloxypropyltrimethoxydecane (KBM503), and 15 parts by weight were added. Tetraethoxydecane (TEOS), 50 parts by weight of titanium tetra-n-butoxide (Ti(OBu) ₄ ), and 150 parts by weight of N-methylpyrrolidone. Thereafter, an aqueous hydrochloric acid solution was added over a period of 30 minutes while stirring at room temperature in a ratio of 0.6 part by weight of 35% hydrochloric acid (hydrochloric acid) and 15 parts by weight of deionized water. Subsequently, the mixture was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and after the completion of the reaction, concentration under reduced pressure was carried out to obtain a polyorganometalloxane solution having a solid content of 30% by weight.

3. Synthesis Example A2~A5

According to the ratio of Table 1, and using the same preparation method as in Synthesis Example A1 The preparation of the synthesis examples A2 to A5 was carried out.

Preparation of polyamidene polymer 1. Synthesis Example B1

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen gas was introduced. 10.01 g of 4,4'-diaminodiphenyl ether and 70 g of N-methylpyrrolidone were added to the four-necked flask, and stirred at room temperature until dissolved; then, 10.91 g of benzene was added. The carboxylic acid dianhydride and 30 g of N-methylpyrrolidone were reacted at room temperature for 6 hours. After the reaction, 97 g of N-methylpyrrolidone, 5.61 g of acetic anhydride and 19.35 g of pyridine were added to the above reaction liquid, and the mixture was heated to 60 ° C, and stirring was continued for 3 hours to carry out a dehydration ring closure reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. The resulting polymer was filtered, and the steps of washing and filtering were repeated three times with methanol. after that, The product was placed in a vacuum oven and dried at a temperature of 60 ° C to obtain a polyamidene-based polymer. The obtained polyfluorene-based polymer was evaluated for the ruthenium yield, and the results are shown in Table 2. Next, 100 parts by weight of a polyimine-based polymer and 1150 parts by weight of N-methylpyrrolidone were uniformly stirred by a shaking stirrer to obtain a polycondensed polyimide polymer solution having a solid content of 8 wt%.

2. Synthesis Example B2~B6

The preparation of Synthesis Examples B2 to B6 was carried out in the same manner as in Synthesis Example B1 according to the ratio of Table 2, and the imidization ratio of the synthesis examples B2 to B6 is shown in Table 2.

Preparation of photocurable polymer 1. Experimental examples 1 to 9

In a three-necked flask having a volume of 500 ml, according to the final composition and ratio shown in Table 3, a synthesis example in various ratio ranges was added, as in Experimental Example 1, 120 parts by weight of the above-mentioned synthesis example A1 polyorganometalloxane solution was added. And 50 parts by weight of the above-mentioned Synthesis Example B1 polyamidene-based polymer solution. Subsequently, the mixture was heated to 60 ° C for heating and stirring for 6 hours, and the solvent was removed by distillation to obtain a photocurable polymer.

100 parts by weight of the photocurable polymer and 1900 parts by weight of N-methylpyrrolidone were uniformly stirred by a stirring stirrer to obtain a photocurable coating composition solution of Experimental Examples 1 to 9 (solid content) : 5 wt%).

2. Comparative Examples 1~6

In a three-necked flask having a volume of 500 ml, according to the final components and ratios shown in Table 4, synthesis examples in various ratio ranges were added. Subsequently, the mixture was heated to 60 ° C for heating and stirring for 6 hours, and the solvent was removed by distillation to obtain a photocurable polymer.

100 parts by weight of the photocurable polymer and 1900 parts by weight of N-methylpyrrolidone were uniformly stirred by a shaking stirrer to obtain a photocurable coating composition solution of Comparative Examples 1 to 6 (solid content) : 5 wt%).

The photocurable coating composition solutions of the above Experimental Examples 1 to 9 and Comparative Examples 1 to 6 were subjected to the following tests, and the results are shown in Tables 3 and 4.

testing method Solution dispersion

The composition solution was placed in a transparent glassware, placed on a black cloth, and visually observed in a state of being illuminated from the upper portion, and evaluated according to the following criteria.

○: The composition solution was transparent and clear.

×: The composition solution has a bulk precipitated substance or the solution is cloudy.

2. Solution coating

The composition solution was filtered under pressure with a membrane filter having a pore size of 0.5 μm to form a coating film on the PI substrate by spin coating. The evaluation was performed based on the following criteria by visual observation.

○: The coating film was flat.

△: The coating film has pinholes.

×: Film formation was impossible.

3. refractive index

The substrate having the coating film obtained by the above-described solution coating property test was placed on a hot plate set to a temperature of 90 ° C, and dried by heating for 5 minutes. Thereafter, the material was solidified using an ultraviolet irradiation device at an energy of 2000 mJ/cm ² at a UV wavelength of 254 nm (light source power of 30 mW/cm ² , manufactured by Keyi, model: AG110-4D-NC) and energy of 3500 mJ/cm ² at a wavelength of 365 nm. After the ultraviolet irradiation (light source power 100 mW/cm ² , manufactured by Eye Graphies, model: UB-011-3A), the substrate was transferred to a hot air circulating oven set to a temperature of 230 ° C, and post-baked for 30 minutes. A photo-curing coating film (having a film thickness of 100 nm) was formed on the substrate. Further, a refractive index at a wavelength of 550 nm was measured using a film measuring instrument (manufactured by Mission Peak Optics Inc., model: MP100-ST).

4. Chemical resistance

The film thickness was measured before the endurance test, and the test piece was immersed in a chemical resistant test solution (1% KOH) at a soaking temperature of 40 ° C and a soaking time of 2 minutes. After immersing, the test piece was taken out, washed with deionized water, and dried under nitrogen, and the film thickness of the test piece after the endurance test was measured.

○: The film thickness reduction ratio was ≦10%.

×: The film thickness reduction ratio was >10%.

5. Hundreds of confidentiality

According to the method of JIS K5600, 100 squares of 10 squares × 10 squares were cut by a cutter on the surface of a 10 cm × 10 cm bulk photo-curing coating film. Thereafter, 600 tapes manufactured by 3M Company were adhered to the surface, and they were peeled off sharply, and evaluated by the number of remaining squares, and the evaluation criteria were as follows.

5B: No squares fall off.

4B: 0% < the number of squares falling off ≦ 5%.

3B: 5% < the number of squares falling off ≦ 15%.

2B: 15% < the number of fallen squares is 5% 35%.

1B: 35% < the number of squares falling off ≦ 65%.

0B: 65% < the number of squares dropped off ≦ 100%.

6. Pencil hardness

The surface of the above-mentioned 10 cm × 10 cm bulk photo-curing coating film was subjected to hardness measurement in accordance with the pencil hardness test of JIS K5600-5-4. The pencil hardness specification is preferably greater than or equal to HB, and more preferably greater than or equal to H.

Table 3

As can be seen from Table 3, the photocurable coating compositions of Experimental Examples 1 to 9 all have good solution dispersibility and solution coating properties, and the obtained photohardenable coating film has a refractive index and a hundred-gram adhesion. , pencil hardness and chemical resistance have a good performance.

On the contrary, in Table 4, the solution dispersibility and the solution coating property of Comparative Example 1 were not good, so that subsequent evaluation was not performed. The coating properties of Comparative Examples 2 and 5 were not good, and in particular, the refractive index of Comparative Example 2 was not good, so neither of them was evaluated. Comparative Examples 3, 4 and 6 have only 3B or less evaluation on the hundred-cell adhesion, and H, H and B on the pencil hardness, respectively; and Comparative Examples 3 and 6 in the chemical resistance. Also underperformed.

In summary, in the photocurable coating composition of the present invention, the polyorganometalloxane structure and the polyamidene structure and the polyamidene structure are contained in a specific range. It has a specific range of ruthenium imidization ratio and constitutes a photocurable polymer. Such a photocurable polymer is excellent in solution dispersibility and solution coating property, and can provide a photohardenable coating which has good adhesion to a PI substrate and which has good refractive index, pencil hardness and chemical resistance. Cloth film.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of protection of the present invention It is subject to the definition of the scope of the patent application attached.

Claims (10)

A photocurable coating composition comprising: a photocurable polymer having a polyorganometalloxane structure and a polyamidene-based structure, wherein the polyorganometallic ruthenium is based on 100 parts by weight of the photocurable polymer The content of the oxyalkylene structure is from 60 parts by weight to 95 parts by weight, the content of the polyamidene structure is from 5 parts by weight to 40 parts by weight; and the ruthenium imidization ratio of the polyamidene structure is 60% to 75%. The photocurable coating composition according to claim 1, wherein the polyorganometalloxane structure is contained in an amount of from 65 parts by weight to 90 parts by weight based on 100 parts by weight of the photocurable polymer. The content of the polyimine structure is from 10 parts by weight to 35 parts by weight. The photocurable coating composition according to claim 2, wherein the polyorganometalloxane structure is contained in an amount of 70 parts by weight to 90 parts by weight based on 100 parts by weight of the photocurable polymer. The content of the polyimine structure is from 10 parts by weight to 30 parts by weight. The photocurable coating composition according to claim 1, wherein the polyamidene structure has a ruthenium amination ratio of 60% to 69%. The photocurable coating composition according to claim 1, further comprising a solvent. The photocurable coating composition according to claim 1, wherein the polyorganometalloxane structure comprises a compound represented by the formula (I), the formula (II) and the formula (III). Addition of a water-decomposition condensation reaction, R ^a ₁ Si(OR ^b ) ₃ (I) In the formula (I), R ^a represents an alkenyl group having 2 to 10 carbon atoms and an alkyl group having 1 to 5 carbon atoms having an acryloxy group. Or an alkyl group having 1 to 5 carbon atoms having a methacryloxy group; R ^b represents an alkyl group having 1 to 5 carbon atoms; Si (OR ^c ) ₄ (II) wherein R ^c represents carbon Number of alkyl groups of 1 to 5; M(OR ^d ) _n (III) In the formula (III), M represents titanium (Ti), cerium (Ta), zirconium (Zr), boron (B), aluminum (Al), Magnesium (Mg) or zinc (Zn), R ^d represents an alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 5; wherein, based on the general formula (I), the general formula (II) and the general formula (III) 100 parts by weight of the compound shown, the compound represented by the formula (I) is contained in an amount of 25 parts by weight to 45 parts by weight, and the compound represented by the formula (II) is contained in an amount of 15 parts by weight to 20 parts by weight, The content of the compound represented by the formula (III) is from 35 parts by weight to 60 parts by weight. The photocurable coating composition according to claim 6, wherein the compound represented by the formula (I) comprises vinyltrimethoxynonane, and at least one selected from the group consisting of 3-methylpropenyloxypropane Trimethoxy decane, 3-methacryl oxiranyl triethoxy decane and 3-propenyl methoxypropyl trimethoxy decane. A photo-curable coating film obtained by the photocurable coating composition according to any one of claims 1 to 7. The photo-curing coating film according to item 8 of the invention of claim 8 has a refractive index of 1.60 to 1.65 at a film thickness of 100 nm. A touch panel comprising the photo-curing coating film according to claim 8 or claim 9.